Dyestuffs containing metals and process of making same



Patented Nov. 24, 1931 u lTEosrArEs SOCIETY on cHn IcAn NnUsTRY IN'BAsLn, :OE'BASEL, swrrznnnnnnfl" nYEsTUFFs co T In'INGMnTALs nlvnrn'oonss OFJMAK'IIINTG sAME-T, i No Drawing. Application filed March 12, 1930, Seria1 No.'435,355, and in Switzerland Maren 1 1929, j l

The present invention relates "to theproduction of new metalliferous dyestuffs. .It comprises the process of making these dyestufis, the dyestuffs themselves, and the ma-' terial that has been dyed with the new dyestuffs. i

. I It has been found that new metalliferous dyestuffs (this term including both the dyestuffs containing only one metal and those 7 containing more than one metal) are obtained by treating thedyestufis which derive from diazotized 5-nitro-2-amino-1-phenols l amino 8 hydroxynaphthalene-monosuland ionic acids of the general formula 0H HR y I v I z: z y p wherein two ws stand for hydrogen and the third as for SO H, and wherein R means hy-' drogen or any acyl residue, with agents yield ing metal capable of forming complex compounds. -Such products are among others the I l-amino-8-hydroxynaphthalene 4 sul- -fonic acid, 1-amino-8-hydroxynaphthalener5- sulfonicacid, 1-amino-8-hydroxynaphtha-' .lene-6-su'lfonic acid, furthersuch as,'for example, the jNracetyL, N-benzoylg N-m'-nitrobenzoyl-, 'N-m-amino-benzoyl, N -sulfo-aryletc. derivatives of these amino-hydroxynaphthalene monosulfonic acids. These dyestufls containingmetals, which may also conta1n several metalscapable of formmg compleXes, such as chromium, copper, iron,man-

ganese, cobalt, nickel, and so forth, are eX- cellently suitable for producing fast tints on ordinary or weighted silk, above all in a neutral or fatty soap bath. This fact is surprising since the corresponding dyestuffs containing metals which derive from the Lamino-8-hydroxynaphthalene-disulfonic acids, show in a neutral or fatty soapb'ath no or but litle aflinity for weighted'silk.

, Furthermore, it i has been found "that equally valuable products containing metals are obtained by conducting the manufacture f the dyestufl in presencefo'f theagents yieldingmetals; I

- amino-l-ph'enol V naphthalene-t-sulfonic 'acid are dissolved in ita obtained by coupling, in solution alkaline with sodium carbonatediazotized 5-nitro-2 and l-aminO-S-hydroxy- 400 parts of water and 2 parts of ammonia,

FRITZ STRA-UB AND HANS MAYER, on znsnnswrmznannlvn; Assielvonsf To g V and the solution is heated to boiling for some,

time together with aquantity of an ammo: niacal copper ,oxlde solution correspondmg with 0.7 part of copper. The whole'is then neutralized with acetic acid, precipitation of the copper compound is completed by adding common salt and thedyestuff is filtered and dried at amoderate'temperature. The dyestufi' is soluble in water to a pure blue-green solution and dyes loaded and not-loaded silk in a neutralbath uniform, pure green-blue tints of equal intensity. 1 f w fWhen instead of l-aminoe8-hydroxynap'hthalenel-sulfonic acid there 'a'reiise'dthe 19-;

808 parts of the dyest ufl obtained byicoupling inan alkaline solution diazotizedfifv 'ainino-8 hydroXynaphthalene-5 or "-e-sur- 5Q "compoundsare obtained which dye silk greennitro-Q-amino-l-phenol and 1 -amino-8-hydroXynaphthalene-t-sulfonic' acid. are dissolved in 500 parts of water.. The solution is heatedto-boiling for 24-30 hours in a reflux apparatus with a quantity of chromium fluoride corresponding-,with 3. 04'palrts of C130 The chromiumEcompoundthus formed is then separated by means of common salt, filtered and dried at amoderate temperature. The dyestufl so obtained is soluble in water to a "bluish-green solution and dyes woolin eral acid bath'green tints, and yields on' natgreen tints.

'v droxynaphthalene--sulfonic Y acid are dissol'Ved in' 500 parts of ater andlthe solution; I is heated to boiling in a reflux apparatus with ura-l silk in an. acetic acid orneutralbath also The correspondlng chrom1fer-' ous dyestufi' obtained from' 5-n1tro-4-chloro 2 amino-1-p'henol yields similar tints 7 Example 5 8.08 "parts ofthedyestuff obtained by couplingjinan alkaline solution diazotized' 5- nitroQ-amino-l-phenol and 1-amino-8-hya quantity of chromium;fluoride, correspond v 3.25 parts of cusO tH O'areaddedandthe ing-with 1.06 parts of Cr O After 24 hours,

liberated mineral acidis neutralized with '1.77 partsof sodium acetate;'while boiling'is continued for a short time." The chromiumcopper compound of the dyestufl thus formed then. separated by means of common salt, filtered, and dried at a'moderate temperature. It issol-uble in Water to a blue-green solution and dyes natural silk in an acetic ,acid or neutral bath blue-green tints. The corresponding. dyestuffs contalning chromium andcopper obtained from 5-111tl'0-4tchloro-2-amino-1-phenol yield similar shades; Similar products are obtained by simultaneously causing chromium and copper com.-;.

pounds to reacton the ,azo-dyestuflt's.'

' 'fia a'mplc 4 V BQOSpart's ofthe lyestufi of'theformula QllQQZOtlZGd 5-.n-i-tro-2-,aminorl pl enol and l- (benzoylamino). 8-hyd-roxy naphthalene-4;-

1 sulfonicacid are dissolvedin' 400 parts of water and the sol ution is heated to. boiling 1. for. 2430;hours in a refluxapparatus WithQO I parts of. a chromiu m fluoride solution correfat dried at a moderate temperature." It is soluble lIl VittGlf to a grey-blue solution: and dyes naturalsrlk in'anacetlc acid or'neutral rjhathreddish-grey tints. I i I I TLlmamjpZ'c/o' Y p 4.46parts' of the dyestu-ff of the formula on lyrrioo i a omj 'SOaH jobtained by couplingin an alkaline solution. d1azot1zed 5-nitro-2-amino-1-phenol and r acetylamino 8 -hydroxy naphthalene sul-o fonic acid are dissolved in 400 parts of Water. The solutionis heated to boiling and mixed with 2.5 parts of crystallized coppersulfate I and 1.4 parts ofcrystallized sodium acetate,

1 boiling being continued for a short time. The copper'compoundthus obtained is then salted V out, filtered and dried; It dyes natural silk in anacetic acid or neutral bath reddish-blue tints. V 3 I I .SFZK;parts ofi the dlyestufi of the; formula V obtained coupling'in an alkaline solution diazotized 5-nitr0A-chlor0-2-amino-l-phenol and -1 amino 8.- hydr,oxy '-'n"aph-thalene-4-sul- =fonic acid aredissol-Ved in N0 parts of water and 5gpartsof: armnoni a and boiling Joli the solution is maintain-ed fm' some timeWh-ile "adding thereto a qu'anti tyio f", an aminon-iacal copper 5 solution obtai-ned from 5 parts of "crystallized copper-sulfat'efand 7 parts'o'f;

ammonia. The copper compound thus formed is salted out, filtered and dried. It

dyes natural silk inan acetic acid or neutral bath greenish-blue tints";

I Example '7. r 8.08 parts of the dyestulf obtained byv cou-'- plin gin anal kaline solutiondiazotized fi-nitro- V -naphthalene 4 sulfonic= acid. are dissolved 1 in 509 parts of Wa ter-and"heated to boiling for,

*a short time'dn'a refluxfapparatus with 5.15 I

parts of' crystallized nickeISulfateEandA parts 'of crystaltl ifzed, sodiumacetatei-q The" nickel 7' compountl of the" dyestuffthus formed is then e V V separated by additionof common-salt, filtered and driedi Itdyesnatural-"si-lkinfa neutral"- bathjgrcen-bt 1e tints} ,1 1 flspondiiigfwith'lfiQ parts ofCr O .The-chromi-um' compound thus formed is then separated by means of common: salhfiltered and 23.9:- parts of lene-l -sulttonic of water and' 30- parts ofica-l'cined sodium" car hon-ate, whereupon the solution'is coupled for some hours at 5 1536; under addition of- 25 parts of crystallinedcopper sulfate withthe diam-compound obtained: in the usual manii n ia l'o S-hydrOXynaphthaid are-dissolved 400 parts eed with the completion of the complex for- 3130 wherein It means hydrogen or an acyl residue,;

mation in an acid medium. The separated dyestuff is filtered off and dried at amoderate temperature. It dissolves in soda to a reddish-blue and in water to a greenish-blue so-- lution, dyeing natural silk in an acetic acid or neutral bath green-blue tints. a

If, for example, nickel or mixtures of copper and nickel are usedinstead of copper," the correspondingnickel or copper-nickel.

compounds are obtained, respectively.

Furthermore, the coupling may also be caustic alkaconducted in an ammoniacal or line medium. 7

What we claim is 1. Process for the manufacture of metalliferous dyestuffs-which consists in treating the wherein two ws stand for hydrogen and the third :0 for SO H, and wherein R means hydrogen or an acyl residue, with agents yielding metals capable of forming complex compounds with the azo-d'yestulfs.

2. Process for the manufacture of metalliferous dyestufis which consists in treating the azo-dyestufi's obtained by alkaline coupling diazotized 5-nitro 2 amino-l-phenols and 1- amino-8-hydr0xynaphthalene-monosulfonic acids of the general formula 0H I IH-R wherein two ws stand for hydrogen and the third 00 for sO Hyand wherein R means hy drogen or an acyl residue, with agents yielding metals oflthe atomic weight between 52 and 64.

3. Process for the manufacture of metallif- I erous dyestuffs which consists in treating the azo-dystuffs obtained by alkaline coupling diazotized 5-nitro-2-amino-l-phenols 'and'f H W c v g g I mon-osul-fom wherein vthe 5-nitrophenolicnucleus may be J further substituted by halogen,-wherein two. j ws stand for hydrogenand the third 1-amino8-hydroxynaphthalene ic acids of the general formula on NH -R I with agents yielding metals weight between 52and 64; a a

a .4; Process'for the manufacture of'metalliferous dyestufls' which consists in treating the azo-dyestuff obtained by alkaline coupling diazotized ic acid of thefo'rmul "on NHi SQaHiii 5. Process for gtheimanufacture of; ma i 1 liferousdyestuifs, which consists in treating the azo-dyestufi obtained by'alkaline coupling diaz'otized a5-nitr0 -2-amino-l-phenol and l amino 8 hydroxynap'hthalene monosulfonic' acid of the formula Y with agents yielding chromium and copper.

6. Process for the manufacture of metalliferous dyestuffs, which consists in treating with agentsyielding copper. i i

5 -nitro -2-amino l-phenol and} lamino-8-hydroxynaphthalenefmonosulfomj;

of -the atomic a v .ZVLBO- In i V I As new-products the metalliferous dye stuffs which contain complex bound metals, e MO-dy 1 which dyestuffs correspond to th stuffs of thegeneral formula Oahl w for SO H, and wherein R- means hydrogen or any acyl residue; and which products form dark powders which dye ordinary or SOaH with agents yielding metals of the atomic weight between 52 and 64.

weighted silk from a neutral or fatty soap bath reddish-grey, red blue to green-blue and green tints;

between-52 an t 61* 17,0

' r i Whril the v ii- Iiit1"0pLig1 li nucleus njay be :t'u 'thr substituted byhalogen; Wherem two' stand for hydrogen and the third 02 for an 'acyl residue, and iyhisl pl ophtts io'rm .icg a k p wd rs hich: cl Ordina y 1 1 W ig 1. 1 V

' y soap [bath] -,bl11end from; neutral, 0;: .7

' W, r d-blue 7 t a semi fl rt i ubstituteclby h ztlogn and Whersin R m egms hydrogen- 01; an @0311 nesidu guand t0 green-blue and green tints.

which p dtluct it p W dlef which and wherei l ims mshydwgenr r 4 1 I wfpjbdusts ti etni etalliferoigs dy stufl's containlng 'meta l s fthe atomicwelght 1, 212. 'As anew predluct-the jmetalliiermis" dyestufi cbntaining'copper which dyesiufi corre sp nds tothe aza-dyesttiff .of'thef-oriilulz B IT Z 10. As new produttsth metallifrciusdye- Stuffs containing metals of the atomic eight 7 V to the azo-dyestqfi fth e formula between 52 and 6 i which dyestufis correspond h tiye'ordih'afl y 01- Weighted silk froma neutral greentilits. i

. 11. ASQGWVP IDd llCtS the metalliferous dyetiUffs contain ng chromium and copper dyer,

I hichdygstuffs tidrres mndto the 220- v pica flirts fcirm i i ildWHiChjiil'QCillCtS form dark powders r nag hes this 28th day of February, 1930.;

vf u

0r fatty wag-bath. i gd blue' 'tbig iean-bhie-and 

